JPH06183712A - Production of fullerenes - Google Patents
Production of fullerenesInfo
- Publication number
- JPH06183712A JPH06183712A JP4286326A JP28632692A JPH06183712A JP H06183712 A JPH06183712 A JP H06183712A JP 4286326 A JP4286326 A JP 4286326A JP 28632692 A JP28632692 A JP 28632692A JP H06183712 A JPH06183712 A JP H06183712A
- Authority
- JP
- Japan
- Prior art keywords
- fullerenes
- inert gas
- soot
- organic solvent
- solid surface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は超導電材料、導電材料、
分離材料、触媒、医用材料などの多方面の用途が期待で
きるフラーレン類を、高純度、高収率かつ連続的に製造
する方法に関する。The present invention relates to a superconductive material, a conductive material,
The present invention relates to a method for continuously producing high-purity, high-yield fullerenes, which are expected to be used in various fields such as separation materials, catalysts and medical materials.
【０００２】[0002]
【従来の技術】化学式がＣx （ｘは60またはそれ以上の
整数）で示されるフラーレン類の合成、分離精製法とし
ては、通常、器壁が冷却され、かつヘリウムガスで置換
された反応容器中で炭素棒をアーク放電させ、生成した
フラーレン類を含有したススを器壁の内側に沈着させ
る。そして反応終了後、反応容器を開け、沈着したスス
をかきとってススを回収し，次いでこのススから溶媒抽
出により所定のフラーレン類を回収するという方法が用
いられている（ネイチャー（Ｎａｔｕｒｅ）、第３４７
巻、３５４頁、１９９０年；ジャーナル・オブ・フィジ
カル・ケミストリィ（Ｊ．Ｐｈｙｓ．Ｃｈｅｍ）、９４
巻、８６３４頁、１９９０年等参照）。2. Description of the Related Art As a method for synthesizing and separating and purifying fullerenes whose chemical formula is represented by C x (x is an integer of 60 or more), a reactor vessel in which the vessel wall is cooled and which is replaced with helium gas is usually used. The carbon rod is arc-discharged therein, and soot containing the generated fullerenes is deposited inside the vessel wall. After completion of the reaction, a method is used in which the reaction vessel is opened, the deposited soot is scraped to recover the soot, and then predetermined fullerenes are recovered from the soot by solvent extraction (Nature, No. 1). 347
Volume, 354, 1990; Journal of Physical Chemistry (J. Phys. Chem), 94.
Vol., Page 8634, 1990, etc.).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
従来の方法ではススを回収する際に、反応器を開けて回
収する必要があり、目的とするフラーレン類と酸素とが
接触し、フラーレン類の一部が酸化されてしまうという
問題点を持つと同時に、製造方法がバッチ式であるた
め、生産性が低いという問題点を有している。However, in the above-mentioned conventional method, when collecting soot, it is necessary to open the reactor for recovery, and the desired fullerene and oxygen come into contact with each other, so that the fullerene At the same time, there is a problem that part of the product is oxidized, and at the same time, there is a problem that productivity is low because the manufacturing method is a batch method.
【０００４】[0004]
【課題を解決するための手段】本発明者らはかかる状況
に鑑み、従来技術の持つ問題点を解決するために鋭意検
討した結果、不活性ガス気流下にフラーレン類を合成
し、その分離、精製工程を不活性ガス雰囲気下にて行う
ことにより上述の問題点を解決できることを見いだし、
本発明に到達した。SUMMARY OF THE INVENTION In view of the above situation, the present inventors have conducted extensive studies to solve the problems of the prior art, and as a result, synthesized fullerenes under an inert gas stream and separated them. It was found that the above-mentioned problems can be solved by performing the refining process in an inert gas atmosphere,
The present invention has been reached.
【０００５】すなわち、本発明は、不活性ガス気流下で
合成したフラーレン類を含有したススを、不活性ガス気
流とともに冷却した固体表面に導き沈着させ、次いで沈
着させたススからフラーレン類が可溶な有機溶媒を用い
てフラーレン類を溶出する工程を含むことを特徴とする
フラーレン類の製造方法にある。また、前記の方法にお
いて、全ての工程を不活性ガス雰囲気下で行うフラーレ
ン類の製造方法にある。That is, according to the present invention, soot containing fullerenes synthesized under an inert gas stream is introduced and deposited on a solid surface cooled with an inert gas stream, and the fullerenes are soluble from the deposited soot. A process for producing fullerenes, which comprises a step of eluting the fullerenes with a different organic solvent. Further, in the above-mentioned method, there is a method for producing fullerenes in which all steps are performed in an inert gas atmosphere.
【０００６】以下に本発明を詳細に説明する。本発明に
おいて製造されるフラーレン類とは化学式がＣX （ｘは
６０またはそれ以上の整数）で表される環状炭素化合物
および、これらのフラーレン類に金属がドープされたも
のも含まれる。金属はフラーレン類の環のなかにドープ
されていても、環の外にドープされていても良い。用い
られる金属は周期律表のＩａ、IIａ、III ａ、III ｂ
族、ランタノイド系列およびアクチノイド系列から選ば
れたものであり、具体的にはＬｉ、Ｎａ、Ｋ、Ｒｂ、Ｃ
ｓ、Ｃａ、Ｙ、Ｓｃ、Ｕ、Ｅｕ、Ｔｌ等を挙げることが
できるが、必ずしもこれらに限定されるものではない。The present invention will be described in detail below. The fullerenes produced in the present invention include cyclic carbon compounds having a chemical formula represented by C X (x is an integer of 60 or more) and those fullerenes doped with a metal. The metal may be doped in the ring of fullerenes or may be doped outside the ring. The metals used are Ia, IIa, IIIa, IIIb of the periodic table.
Group selected from the group consisting of lanthanoid series and actinoid series, and specifically, Li, Na, K, Rb, C
Examples thereof include s, Ca, Y, Sc, U, Eu, and Tl, but are not necessarily limited thereto.
【０００７】フラーレン類の合成方法に関しては、例え
ば、前記の文献に記載されているような炭素のアーク放
電等の公知の方法でフラーレン類を含有するススを生成
する方法が代表的なものであるが、この方法に限定され
ず、ススの中にフラーレン類を含有しているものを得る
方法であれば、他の方法でも良い。通常、炭素のアーク
放電によって得られるススはフラーレン類以外に平面状
の炭素化合物や炭化水素化合物などを含有しているが、
適当な有機溶媒を選択することにより、溶媒抽出法や液
体クロマトグラフィー法により、フラーレン類を選択的
に分離することができる。A typical method of synthesizing fullerenes is a method of producing soot containing fullerenes by a known method such as carbon arc discharge as described in the above-mentioned document. However, the method is not limited to this, and any other method may be used as long as it is a method of obtaining a soot containing fullerenes. Usually, soot obtained by arc discharge of carbon contains planar carbon compounds and hydrocarbon compounds in addition to fullerenes,
By selecting an appropriate organic solvent, fullerenes can be selectively separated by a solvent extraction method or a liquid chromatography method.
【０００８】本発明の合成、沈着、溶出等の一連の工程
はすべて不活性ガス雰囲気下で連続的に行うことができ
る。特に、フラーレン類は酸素によって酸化され易いの
で不活性ガス中の酸素はできるだけ除いておくことが好
ましく、また水分等もできるだけ除去しておくことが好
ましい。The series of steps such as synthesis, deposition and elution according to the present invention can be continuously carried out in an inert gas atmosphere. Particularly, since fullerenes are easily oxidized by oxygen, it is preferable to remove oxygen in the inert gas as much as possible, and it is preferable to remove water and the like as much as possible.
【０００９】本発明で用いられる不活性ガスは、生成し
たフラーレン類と反応しないものであれば特に限定はな
くヘリウム、アルゴン、または窒素等を用いることがで
きるが、フラーレン類の生成率が高いことからアーク放
電時はヘリウムを用いることが特に好ましい。The inert gas used in the present invention is not particularly limited as long as it does not react with the produced fullerenes, and helium, argon, nitrogen or the like can be used, but the production rate of fullerenes is high. Therefore, it is particularly preferable to use helium during arc discharge.
【００１０】生成したススは、不活性ガス気流とともに
冷却装置に導かれ、装置内の冷却された固体表面に沈着
される。この場合、固体表面は０℃以下、好ましくは−
２０℃以下に冷却されていることが必要である。また、
用いられる固体表面の素材としては特に限定はなく、金
属、ガラス、セラミックス、プラスチック等のいずれを
も用いることができるが、熱伝導率などの点からは金
属、例えば鉄、銅、アルミニウム、ステンレス鋼等の金
属あるいは合金を用いることが特に好ましい。The soot produced is introduced into a cooling device together with an inert gas stream and deposited on the cooled solid surface in the device. In this case, the solid surface has a temperature of 0 ° C. or lower, preferably −
It must be cooled to 20 ° C or lower. Also,
The solid surface material used is not particularly limited, and any of metals, glass, ceramics, plastics and the like can be used, but from the viewpoint of thermal conductivity, metals such as iron, copper, aluminum and stainless steel are used. It is particularly preferable to use a metal or alloy such as
【００１１】本発明で用いられる冷却装置の形状には特
に限定はないが、通常は内部を冷媒により冷却された円
筒形状のものを用いることが好ましい。The shape of the cooling device used in the present invention is not particularly limited, but normally it is preferable to use a cylindrical one whose inside is cooled by a refrigerant.
【００１２】本発明で用いられる有機溶媒はフラーレン
類が可溶なものであれば特に限定はないが、具体的には
芳香族炭化水素、二硫化炭素、ピリジン、キノリンの単
独溶媒または混合溶媒等が例示される。芳香族炭化水素
の具体例としてはベンゼン、トルエン、キシレンまたは
それらの誘導体を挙げることができる。The organic solvent used in the present invention is not particularly limited as long as it is a solvent in which fullerenes are soluble, and specific examples thereof include aromatic hydrocarbons, carbon disulfide, pyridine and quinoline alone or mixed solvents. Is exemplified. Specific examples of the aromatic hydrocarbon include benzene, toluene, xylene or their derivatives.
【００１３】本発明においてフラーレン類は、かかる溶
媒を用いて上記のススから溶出し、更に必要に応じて得
られる溶液からソックスレー抽出法等の溶媒抽出法また
は液体クロマトグラフィー法等の公知の方法で分離、精
製することができる。In the present invention, the fullerenes are eluted from the soot by using such a solvent, and if necessary, a solution obtained by a known method such as a solvent extraction method such as Soxhlet extraction method or a liquid chromatography method. It can be separated and purified.
【００１４】本発明のフラーレンの製造方法で用いる装
置の一例を示した系統図を図１に示す。図１中、反応器
１内において、不活性ガスの導入口２から導入される不
活性ガスの存在下に炭素棒３のアーク放電で生成したス
スは、前述の不活性ガスの気流とともに冷却装置４に運
ばれ、冷却された固体表面５に沈着する。次いで有機溶
媒タンク６を加熱して発生させた有機溶媒蒸気を冷却装
置４内に導入して液化させた有機溶媒によりススを溶出
し、フラーレン類を含む溶出液は試料回収容器７に回収
される。このようにして得られた溶出液を前述の公知の
方法を用いて分離、精製を行うことにより、フラーレン
類が製造される。A system diagram showing an example of an apparatus used in the method for producing fullerenes of the present invention is shown in FIG. In FIG. 1, in the reactor 1, the soot produced by the arc discharge of the carbon rod 3 in the presence of the inert gas introduced from the inlet 2 for the inert gas is the cooling device together with the above-mentioned inert gas flow. 4 and is deposited on the cooled solid surface 5. Then, the organic solvent vapor generated by heating the organic solvent tank 6 is introduced into the cooling device 4 and the soot is eluted by the liquefied organic solvent, and the eluate containing the fullerenes is recovered in the sample recovery container 7. . The fullerene is produced by separating and purifying the eluate thus obtained using the above-mentioned known method.
【００１５】[0015]
【実施例】以下に、本願発明について代表的な例を示し
さらに具体的に説明する。なお、これらは説明のための
単なる例示であって、本発明はこれらに何ら限定される
ものでないことは言うまでもない。The present invention will be described in more detail below by showing typical examples. Needless to say, these are merely examples for description and the present invention is not limited to these.
【００１６】実施例１ 反応器のほぼ中央に炭素棒を設置した。反応器はいった
ん減圧した後、高純度のヘリウムガスをバルブを通して
３０ l／ｍｉｎの流量で連続的に流した。次いで炭素棒
を１ｍｍの距離まで近づけ、２５Ｖ−２００Ａで直流ア
ーク放電を行った。このようにして生成したフラーレン
類を含有したススは、ヘリウムガス気流とともに冷却装
置に導かれ、装置内の冷却した固体表面に沈着した。こ
の固体表面はステンレス鋼製で、円筒状をしており、そ
の内部を液体窒素により冷却されていた。Example 1 A carbon rod was installed at approximately the center of the reactor. After depressurizing the reactor once, high-purity helium gas was continuously flowed through the valve at a flow rate of 30 l / min. Next, the carbon rod was brought close to a distance of 1 mm, and DC arc discharge was performed at 25V-200A. The soot containing the fullerenes thus produced was introduced into the cooling device together with the helium gas flow and deposited on the cooled solid surface in the device. The solid surface was made of stainless steel and had a cylindrical shape, and the inside thereof was cooled by liquid nitrogen.
【００１７】前記の方法により２時間アーク放電するこ
とにより炭素３０ｇが消費された。このようにして生成
したススが冷却した固体表面に沈着した後、予めトルエ
ンを仕込んだ溶媒タンクを加熱して、トルエン蒸気を冷
却装置内に導入した。トルエン蒸気は冷却した固体表面
に接触すると同時に液化して上部から液体となって流下
し、固体表面に沈着したススの大部分を同伴して下部に
設置した試料容器に集められた。集めたフラーレン類を
含有したススを窒素雰囲気下でソックスレー抽出器を用
いて１０時間トルエン抽出した。得られた抽出液からト
ルエンを減圧留去後真空乾燥して、黒色のフラーレン粉
末４．７ｇを得た（フラーレン類の生成率は１６％であ
った）。30 g of carbon was consumed by arcing for 2 hours according to the method described above. After the soot generated in this way was deposited on the cooled solid surface, the solvent tank preliminarily charged with toluene was heated to introduce the toluene vapor into the cooling device. The toluene vapor contacted the cooled solid surface and was liquefied at the same time to become a liquid from the upper part, which flowed down, and together with most of the soot deposited on the solid surface, was collected in a sample container installed in the lower part. The soot containing the collected fullerenes was subjected to toluene extraction for 10 hours using a Soxhlet extractor under a nitrogen atmosphere. Toluene was distilled off under reduced pressure from the obtained extract and then vacuum dried to obtain 4.7 g of a black fullerene powder (the production rate of fullerenes was 16%).
【００１８】また、得られたフラーレン類を高速液体ク
ロマトグラフィーおよび質量分析により分析したとこ
ろ、酸素とフラーレン類の反応物等の不純物は検出され
なかった。When the obtained fullerenes were analyzed by high performance liquid chromatography and mass spectrometry, impurities such as a reaction product of oxygen and fullerenes were not detected.
【００１９】実施例２ 実施例１で用いた炭素棒に替えて、５重量％のランタン
金属を均一に分散させた炭素棒を用いた以外は実施例１
と全く同一の条件および方法でフラーレン類の製造を行
った。この結果、得られたフラーレン類の生成率は１８
％であった。また、実施例１と同様の方法で、得られた
フラーレン類の分析を行った結果、フラーレン中に３．
６％のランタン含有フラーレンが存在することが確認さ
れた。Example 2 Example 1 was repeated except that the carbon rod used in Example 1 was replaced with a carbon rod in which 5% by weight of lanthanum metal was uniformly dispersed.
Fullerenes were produced under exactly the same conditions and method. As a result, the production rate of the obtained fullerenes was 18
%Met. In addition, as a result of analyzing the obtained fullerenes by the same method as in Example 1, 3.
It was confirmed that 6% lanthanum-containing fullerenes were present.
【００２０】比較例１ 反応器の上部が蓋により完全に密閉されているものを使
用した以外は実施例１と同様の条件で同一時間アーク放
電を行った。このとき、生成したフラーレン類を含有す
るススは、反応器の内壁に付着した。所定の時間アーク
放電を行った後、上部の蓋を開けて、反応器の内壁に付
着したススをかきとり捕集した。このススを、実施例１
と同様に窒素雰囲気下でソックスレー抽出器を用いてト
ルエン抽出した結果、フラーレン類が４．１ｇ回収され
た。しかし、得られたフラーレン類を実施例１と同一の
方法で分析したところ、２８重量％が酸素との反応物で
あったため、この方法におけるフラーレン類の生成率は
９．８％となった。Comparative Example 1 Arc discharge was performed for the same time under the same conditions as in Example 1 except that a reactor whose upper portion was completely sealed with a lid was used. At this time, the soot containing the generated fullerenes adhered to the inner wall of the reactor. After performing arc discharge for a predetermined time, the upper lid was opened and the soot adhering to the inner wall of the reactor was scraped off and collected. This soot is used in Example 1.
As a result of extracting with toluene using a Soxhlet extractor under a nitrogen atmosphere in the same manner as above, 4.1 g of fullerenes were recovered. However, when the obtained fullerenes were analyzed by the same method as in Example 1, 28% by weight was a reaction product with oxygen, so that the production rate of fullerenes by this method was 9.8%.
【００２１】比較例２ 実施例２で用いた炭素棒を用いた以外は比較例１と全く
同様の条件でフラーレン類の製造を行った。得られたフ
ラーレン類を実施例１と同様の方法で分析したところ、
得られたフラーレン類中のランタン含有フラーレンの割
合は０．２％であった。Comparative Example 2 Fullerenes were produced under the same conditions as in Comparative Example 1 except that the carbon rod used in Example 2 was used. When the obtained fullerenes were analyzed by the same method as in Example 1,
The ratio of lanthanum-containing fullerenes in the obtained fullerenes was 0.2%.
【００２２】[0022]
【発明の効果】本発明のフラーレン類の製造方法によれ
ば、連続的にフラーレン類を製造することができるた
め、その生産性を大幅に向上させることができる。さら
に、完全に酸素を遮断した状態でフラーレン類を製造す
ることが可能なため、酸素とフラーレン類の反応物の生
成を防ぎ、純度の高いフラーレン類を高収率で製造する
ことができる。According to the method for producing fullerenes of the present invention, since fullerenes can be continuously produced, the productivity can be greatly improved. Furthermore, since it is possible to produce fullerenes in a state where oxygen is completely blocked, it is possible to prevent the formation of a reaction product of oxygen and fullerenes and produce fullerene with high purity in a high yield.
【図１】本発明の製造方法に用いる製造装置の一例を構
成する系統図である。FIG. 1 is a system diagram that constitutes an example of a manufacturing apparatus used in a manufacturing method of the present invention.
【符号の説明】 １ 反応器 ２ 不活性ガスの導入口 ３ 炭素棒 ４ 冷却装置 ５ 固体表面 ６ 有機溶媒タンク ７ 試料回収容器[Explanation of Codes] 1 Reactor 2 Inlet gas inlet 3 Carbon rod 4 Cooling device 5 Solid surface 6 Organic solvent tank 7 Sample recovery container
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂東 俊治 愛知県岡崎市明大寺町西郷中38 分子科学 研究所内 (72)発明者 水谷 伸雄 愛知県岡崎市明大寺町西郷中38 分子科学 研究所内 (72)発明者 永田 正明 愛知県岡崎市明大寺町西郷中38 分子科学 研究所内 (72)発明者 三谷 忠興 愛知県岡崎市明大寺町西郷中38 分子科学 研究所内 (72)発明者 丸山 有成 愛知県岡崎市明大寺町西郷中38 分子科学 研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shunji Bando, 38, Saigochu, Myodaiji-cho, Okazaki, Aichi Prefecture (72) Inventor Nobuo Mizutani, 38, Saigochu, Myodaiji-cho, Okazaki, Aichi (Institute for Molecular Science) 72) Inventor Masaaki Nagata 38, Saigochu, Myodaiji-cho, Okazaki-shi, Aichi (72) Inventor Tadaoki Mitani 38 Saigochu, Myodaiji-cho, Okazaki-shi, Aichi (72) Inventor, Ariari Maruyama 38 Saigochu, Myodaiji-cho, Okazaki-shi, Japan Inside the Institute for Molecular Science
Claims (5)
したススを生成させ、次いでこのススを、不活性ガス気
流とともに冷却した固体表面に導き沈着させ、次いで沈
着させたススからフラーレン類が可溶な有機溶媒を用い
てフラーレン類を溶出する工程を含むことを特徴とする
フラーレン類の製造方法。1. A soot containing fullerenes is generated under an inert gas flow, and the soot is then introduced together with an inert gas flow onto a cooled solid surface for deposition, and then the deposited soot can be converted into fullerenes. A method for producing fullerenes, comprising the step of eluting the fullerenes with a soluble organic solvent.
ことを特徴とする請求項１記載のフラーレン類の製造方
法。2. The method for producing fullerenes according to claim 1, wherein all steps are performed in an inert gas atmosphere.
窒素であることを特徴とする請求項１または請求項２記
載のフラーレン類の製造方法。3. The method for producing fullerenes according to claim 1 or 2, wherein the inert gas is helium, argon or nitrogen.
却された円筒形状物の表面であることを特徴とする請求
項１乃至請求項３記載のフラーレン類の製造方法。4. The method for producing fullerenes according to claim 1, wherein the cooled solid surface is the surface of a cylindrical object whose interior is cooled by a refrigerant.
を特徴とする請求項１乃至請求項４記載のフラーレン類
の製造方法。5. The method for producing fullerenes according to claim 1, wherein the fullerenes contain a metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4286326A JPH06183712A (en) | 1992-10-23 | 1992-10-23 | Production of fullerenes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4286326A JPH06183712A (en) | 1992-10-23 | 1992-10-23 | Production of fullerenes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06183712A true JPH06183712A (en) | 1994-07-05 |
Family
ID=17702942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4286326A Pending JPH06183712A (en) | 1992-10-23 | 1992-10-23 | Production of fullerenes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06183712A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07237913A (en) * | 1994-02-25 | 1995-09-12 | Agency Of Ind Science & Technol | Method and device for producing fullerene |
| JPH07237912A (en) * | 1994-02-28 | 1995-09-12 | Univ Nagoya | Method for producing fullerene compounds and device for producing the same |
| JPH10265206A (en) * | 1997-03-26 | 1998-10-06 | Satoru Mieno | Continuous synthesis of fullerene made of lumpy carbon raw material and device therefor |
| JP2002255524A (en) * | 2001-03-01 | 2002-09-11 | Sony Corp | Method and apparatus for producing carbonaceous material |
| WO2003106337A1 (en) * | 2002-06-18 | 2003-12-24 | Motorola, Inc. | Non-destructive separation of nanomorphic carbon species |
| WO2004040678A1 (en) * | 2002-10-31 | 2004-05-13 | Mitsubishi Chemical Corporation | Additive to positive electrode material for lithium secondary battery, positive electrode material for lithium secondary battery and, prepared from the positive electrode material, positive electrode and lithium secondary battery |
| WO2004054926A1 (en) * | 2002-12-16 | 2004-07-01 | Ideal Star Inc. | Involved fullerene manufacturing and collecting system tool |
| WO2005014476A1 (en) * | 2003-08-08 | 2005-02-17 | Nec Corporation | Apparatus for producing nanocarbon, method for producing nanocarbon and method for collecting nanocarbon |
| KR100491702B1 (en) * | 2001-10-04 | 2005-05-27 | 캐논 가부시끼가이샤 | Method for producing fullerenes |
| JP2005150410A (en) * | 2003-11-17 | 2005-06-09 | Japan Science & Technology Agency | Thin film transistor |
| KR100661008B1 (en) * | 2003-03-26 | 2006-12-26 | 캐논 가부시끼가이샤 | Production process of nano carbon material |
| KR100903857B1 (en) * | 2007-11-28 | 2009-06-24 | 충남대학교산학협력단 | A method for manufacturing carbon nanotubes for field emission devices and carbon nanotubes for field emission device obtained from this method |
| US9187328B2 (en) | 2009-03-03 | 2015-11-17 | Isis Innovation Limited | Methods and apparatus for the production of carbon-containing materials |
-
1992
- 1992-10-23 JP JP4286326A patent/JPH06183712A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07237913A (en) * | 1994-02-25 | 1995-09-12 | Agency Of Ind Science & Technol | Method and device for producing fullerene |
| JPH07237912A (en) * | 1994-02-28 | 1995-09-12 | Univ Nagoya | Method for producing fullerene compounds and device for producing the same |
| JPH10265206A (en) * | 1997-03-26 | 1998-10-06 | Satoru Mieno | Continuous synthesis of fullerene made of lumpy carbon raw material and device therefor |
| JP2002255524A (en) * | 2001-03-01 | 2002-09-11 | Sony Corp | Method and apparatus for producing carbonaceous material |
| KR100491702B1 (en) * | 2001-10-04 | 2005-05-27 | 캐논 가부시끼가이샤 | Method for producing fullerenes |
| WO2003106337A1 (en) * | 2002-06-18 | 2003-12-24 | Motorola, Inc. | Non-destructive separation of nanomorphic carbon species |
| US7029645B2 (en) | 2002-06-18 | 2006-04-18 | Motorola, Inc. | Method for non-reactive separation of nanomorphic carbon species |
| WO2004040678A1 (en) * | 2002-10-31 | 2004-05-13 | Mitsubishi Chemical Corporation | Additive to positive electrode material for lithium secondary battery, positive electrode material for lithium secondary battery and, prepared from the positive electrode material, positive electrode and lithium secondary battery |
| WO2004054926A1 (en) * | 2002-12-16 | 2004-07-01 | Ideal Star Inc. | Involved fullerene manufacturing and collecting system tool |
| KR100661008B1 (en) * | 2003-03-26 | 2006-12-26 | 캐논 가부시끼가이샤 | Production process of nano carbon material |
| WO2005014476A1 (en) * | 2003-08-08 | 2005-02-17 | Nec Corporation | Apparatus for producing nanocarbon, method for producing nanocarbon and method for collecting nanocarbon |
| JP2005150410A (en) * | 2003-11-17 | 2005-06-09 | Japan Science & Technology Agency | Thin film transistor |
| KR100903857B1 (en) * | 2007-11-28 | 2009-06-24 | 충남대학교산학협력단 | A method for manufacturing carbon nanotubes for field emission devices and carbon nanotubes for field emission device obtained from this method |
| US9187328B2 (en) | 2009-03-03 | 2015-11-17 | Isis Innovation Limited | Methods and apparatus for the production of carbon-containing materials |
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